Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/91—Graft copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P17/00—Drugs for dermatological disorders
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/59—Mixtures
  • A61K2800/594—Mixtures of polymers

Definitions

• the present invention relates to a cosmetic or dermatological composition for the treatment of keratin materials, in particular human hair, comprising at least one grafted silicone polymer comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, the one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain and at least one thickening polymer or copolymer of (meth) acrylamide or of a (meth) acrylamide derivative as well as its applications.
• Polymers of the grafted silicone polymer type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted onto said " main chain are known for their styling properties. They are particularly advantageous in hair cosmetics because they provide hold to the hair. Their cosmetic properties after application to the hair are nevertheless insufficient. It is noted that the hair exhibits, after application of these polymers, a rough feel and crunching resulting from a discontinuous distribution of the polymer along the hair fibers.
• the Applicant has surprisingly found that the use of a thickening polymer or copolymer of (meth) acrylamide or of a derivative of (meth) acrylamide, crosslinked or non-crosslinked in hair compositions containing a polymer of the silicone polymer type grafted comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted onto said main chain, made it possible to improve, on application , depositing the grafted silicone polymer along the keratin fibers and improving their cosmetic properties, in particular in terms of feel while retaining the styling properties of the grafted silicone polymer.
• composition according to the invention is therefore essentially characterized by the fact that it contains in a cosmetically or demnatologically acceptable medium at least one grafted silicone polymer comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain and at least one thickening polymer or copolymer of (meth) acrylamide or of a (meth) acrylamide derivative, crosslinked or non-crosslinked.
• the silicone polymers grafted according to the invention are preferably chosen from polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane, polymers with a polysiloxane skeleton grafted with non-silicone organic monomers and their mixtures
• sicone or polysiloxane is intended to denote, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensation of silanes suitably functionalized, and essentially consisting of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond
• hydrocarbon radicals being directly linked via a carbon atom on said silicon atoms.
• the most common hydrocarbon radicals are alkyl radicals, in particular d-C 10 and in particular methyl, fluoroalkyl radicals, aryl radicals and in particular phenyl, and alkenyl radicals and in particular vinyl, other types of radical capable of be linked either directly or via a hydrocarbon radical to the siloxane chain are in particular hydrogen, halogens and in particular chlorine, bromine or fluorine, thiols, alkoxy radicals, radicals polyoxyalkylenes (or polyethers) and in particular polyoxyethylene and / or polyoxypropylene, hydroxyl or hydroxyalkyl radicals, substituted or unsubstituted amine groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals, quaternary ammonium groups, amphoteric or
• polysiloxane macromer is intended to denote, in accordance with general acceptance, any monomer containing in its structure a polymer chain of the polysiloxane type.
• the polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane in accordance with the present invention consist of an organic main chain formed from organic monomers not containing silicone, on which is grafted, inside of said chain as well as optionally at at least one of its ends, at least one polysiloxane macromer.
• the non-silicone organic monomers constituting the main chain of the grafted silicone polymer can be chosen from ethylenically unsaturated monomers which can be polymerized by the radical route, polycondensation polymerizable monomers such as those forming polyamides, polyesters, polyurethanes, opening monomers such as those of the oxazoline or caprolactone type.
• the polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane in accordance with the present invention can be obtained by any means known to those skilled in the art, in particular by reaction between (i) a starting polysiloxane macromer correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, themselves correctly functionalized by a function which is capable of reacting with the functional group or groups carried by said silicone by forming a covalent bond; a classic example of such a reaction is the radical reaction between a vinyl group carried on one of the ends of the silicone with a double bond of an ethylenically unsaturated monomer of the main chain.
• the polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane are more preferably chosen from those described in patents US 4,693,935, US 4,728,571 and US 4,972,037 and patent applications EP-A-0412704 , EP-A-0412707, EP-A-0640105 and WO 95/00578. These are copolymers obtained by radical polymerization from ethylenically unsaturated monomers and silicone macromers having a terminal vinyl group or else copolymers obtained by reaction of a polyolefin comprising functionalized groups and of a polysiloxane macromer having a function. terminal reactive with said functionalized groups.
• a particular family of grafted silicone polymers suitable for carrying out the present invention consists of silicone graft copolymers comprising: a) from 0 to 98% by weight of at least one lipophilic monomer (A) of low lipophilic polarity with ethylenic unsaturation , polymerizable by the radical route; b) from 0 to 98% by weight of at least one polar hydrophilic monomer (ethylenically unsaturated), copolymerizable with the monomer (s) of type (A) c) from 0.01 to 50% by weight of at least a polysiloxane macromer (C) of general formula: or :
• X denotes a vinyl group copolymerizable with the monomers (A) and (B);
• Y denotes a divalent linking group
• R denotes hydrogen, C ⁇ -C 6 alkyl or alkoxy, C 6 -C ⁇ 2 aryl;
• Z denotes a monovalent polysiloxane unit having a number average molecular weight of at least 500; n is 0 or 1 and m is an integer ranging from 1 to 3; the percentages being calculated relative to the total weight of the monomers (A), (B) and (C).
• EP-A-0412704, EP-A-0412707, EP-A-0640105 have a number average molecular weight preferably ranging from 10,000 to 2,000,000 and preferably a glass transition temperature Tg or a crystalline melting temperature Tm of at least
• lipophilic monomers (A) there may be esters of acrylic or methacrylic acid of CrC- ⁇ 8 alcohols; styrene; polystyrene macromers; vinyl acetate; vinyl propionate; alpha-methylstyrene; tertiary butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; esters of acrylic or methacrylic acid and of 1, 1-dihydroperfluoroalkanol or of its counterparts; esters of acrylic or methacrylic acid and omega-hydrydofluroalkanol; esters of acrylic or methacrylic acid and fluoroalkylsulfoamido alcohol; esters of acrylic or methacrylic acid and alcohol fluoroalkyl; esters of acrylic or methacrylic acid and alcohol fluoride; or their mixtures.
• the preferred monomers (A) are chosen from the group consisting of n-butyl methacrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, methacrylate methyl, 2- (N-methyl perflurooctane sulfonamido) -ethylacrylate; 2- (N-butyl-perflurooctane sulfonamido) -ethylacrylate and their mixtures.
• polar monomers (B) examples include acrylic acid, methacrylic acid, NN-dimethylacrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl quaternized methacrylate, (meth) acrylamide, Nt-butylacrylamide, l maleic acid, maleic anhydride and their half-esters, hydroxyalkylated (meth) acrylates, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinylpyridine, vinylimidazole, vinyl heterocyciic polar compounds , styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam or mixtures thereof.
• the preferred monomers (B) are chosen from the group consisting of acrylic acid, N, N- dimethylacrylamide, methacrylate dimethylaminoethyl, dimethylaminoethyl methacrylate quaternizes, vinyipyrrolidone and their mixtures.
• the preferred polysiloxane macromers (C) of formula (I) are chosen from those corresponding to the following general formula (II):
• R 1 is hydrogen or -COOH (preferably hydrogen);
• R 2 is hydrogen, methyl or -CH 2 COOH (preferably methyl);
• R 3 is alkyl, alkoxy or alkylamino in CrC 6 , aryl in Ce-C ⁇ 2 or hydroxyl (preferably methyl);
• R 4 is alkyl, alkoxy or alkylamino, C r C 6 aryl, C 6 -C 12 alkyl or hydroxyl (preferably methyl);
• q is an integer from 2 to 6 (preferably 3);
• p is 0 or 1;
• r is an integer from 5 to 700;
• m is an integer ranging from 1 to 3 (preferably 1);
• CH 2 ⁇ - -CO-CCHA— Si— O -Si-0 hSi— (CH 2 ) 3 -CH 3
• n a number ranging from 5 to 700.
• CH 2 CC-0 - (CH 2 ) 3 - -Si - O- -Si-0 f-Si - (CH 2 ) 3 -CH
• n a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
• n a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
• silicone polymers suitable for carrying out the present invention consists of silicone graft copolymers capable of being obtained by reactive extrusion of a polysiloxane macromer having a terminal reactive function on a polymer of the polyolefin type comprising reactive groups capable of reacting with the terminal function of the polysiloxane macromer to form a covalent bond allowing the grafting of the silicone onto the main chain of the polyolefin.
• the reactive polyolefins are preferably chosen from polyethylenes or polymers of monomers derived from ethylene such as propylene, styrene,
• They are chosen more particularly from copolymers of ethylene or of derivatives of ethylene and of monomers chosen from those comprising a carboxylic function such as (meth) acrylic acid; those comprising an acid anhydride function such as maleic acid anhydride; those comprising an acid chloride function such as (meth) acrylic acid chloride; those comprising an ester function such as the esters of (meth) acrylic acid; those comprising an isocyanate function.
• the silicone macromers are preferably chosen from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or near the end of said chain, chosen from the group consisting of alcohols, thiols, epoxies, primary amines and secondary and more particularly among those corresponding to the general formula (III):
• T is chosen from the group consisting of NH2, NHR ', an epoxy function, OH, SH; R 5, R 5, R 7 and R 'independently denote an alkyl, C ⁇ -C 6 alkyl, phenyl, benzyl or alkylphenyl Ce-C ⁇ , hydrogen; s is a number from 2 to 100; t is a number from 0 to 1000 and y is a number from 1 to 3. They have a weight number average molecular preferably ranging from 5,000 to 300,000, more preferably from 8,000 to 200,000 and more particularly from 9,000 to 40,000.
• the grafted silicone polymer (s) with a polysiloxane backbone grafted with non-silicone organic monomers comprise a main silicone chain (or polysiloxane (sSi-O-) n ) on which is grafted, inside of said chain as well as optionally at at least one of its ends, at least one organic group not comprising silicone.
• the silicone polymer, with a polysiloxane backbone grafted with non-silicone organic monomers used comprises the result of radical copolymerization between on the one hand at least one nonionic anionic organic monomer -silicon having ethylenic unsaturation and / or a non-silicone hydrophobic organic monomer having ethylenic unsaturation and on the other hand a silicone having in its chain at least one functional group capable of reacting on said ethylenic unsaturations of said non-silicone monomers by forming a covalent bond, in particular thio-functional groups.
• said anionic monomers containing ethylenic unsaturation are preferably chosen, alone or in mixtures, among the unsaturated, linear or branched carboxylic acids, optionally partially or totally neutralized in the form of a salt, this or these unsaturated carboxylic acids may more particularly be acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid.
• Suitable salts are especially the alkali, alkaline earth and ammonium salts.
• the organic group of anionic nature which comprises the result of the (homo) radical polymerization of at least one anionic monomer of the unsaturated carboxylic acid type can be, after reaction, post-neutralized with a base (soda, ammonia, ...) to bring it in the form of a salt.
• the hydrophobic ethylenically unsaturated monomers are preferably chosen, alone or as a mixture, from acrylic acid alkanol esters and / or methacrylic acid esters from alkanols.
• the alkanols are preferably in C ⁇ -C ⁇ 8 and more particularly in C r C 12 .
• the preferred monomers are chosen from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate isopentyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate or mixtures thereof.
• a family of silicone polymers with a polysiloxane backbone grafted with non-silicone organic monomers which are particularly suitable for implementing the present invention consists of silicone polymers comprising in their structure the following unit of formula (IV):
• the Gi radicals identical or different, represent hydrogen or a C 1 -C 10 alkyl radical or also a phenyl radical;
• the radicals G 2 which are identical or different, represent a C 1 -C 10 alkylene group,
• G 3 represents a polymer residue resulting from r (homo) polymé ⁇ sat ⁇ on of at least one anionic monomer with ethylenic unsaturation,
• G 4 represents a polymer residue resulting from (homo) polymerization of at least one hydrophobic ethylenically unsaturated monomer, m and n are equal to O or 1
• a is an integer ranging from 0 and 50
• b is an integer which can be between 10 and 350
• c is a number integer ranging from 0 and 50, provided that one of the parameters a and c is different from 0
• the motif of formula (IV) above has at least one, and even more preferably all, of the following characteristics:
• radicals d denote an alkyl radical, preferably the methyl radical
• radicals G 2 represent a divalent radical in C r C 3 , preferably a propylene radical
• - G 3 represents a polymé ⁇ que radical resulting from the (homo) polymé ⁇ sat ⁇ on of at least one monomer of the type ethylenically unsaturated carboxylic acid, preferably acrylic acid and / or methacrylic acid,
• G 4 represents a polymer radical resulting from the (homo) polymé ⁇ sat ⁇ on of at least one monomer of the (meth) acrylate type of alkyl (CrC ⁇ o), preferably isobutyl or methyl (meth) acrylate
• grafted silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxanes (PDMS) on which are grafted, via a connecting link of thiopropylene type, mixed polymer units of the poly (meth) acid type acrylic and poly (meth) methyl acrylate type
• PDMS polydimethylsiloxanes
• grafted silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxanes (PDMS) onto which are grafted, poly (meth) type polymer units, via a thiopropylene-type connecting link isobutyl acrylate
• PDMS polydimethylsiloxanes
• the number-average molecular mass of the silicone polymers with a polysiloxane backbone grafted with non-silicone organic monomers of the invention varies from approximately 10,000 to 1,000,000, and even more preferably from approximately 10,000 to 100,000
• the silicone graft polymers of the invention are preferably used in an amount ranging from 0.01 to 20% by weight of the total weight of the composition. More preferably, this amount varies from 0.1 to 15% by weight and even more preferably from 0.5 to 10% by weight.
• copolymers of ammonium acrylate and (meth) acrylamide, crosslinked or non-crosslinked such as the product sold under the name BOZEPOL C NEW or the product PAS 5193 sold by the company HOECHST (they are described and prepared in documents FR 2416723, USP2798053 and USP 2923692);
• the polymers or copolymers of (meth) acrylamide or of a (meth) acrylamide derivative according to the invention are used in an amount ranging from 0.01 to 20% by weight of the total weight of the composition. More preferably, this amount varies from 0.1 to 15% by weight and even more preferably from 0.5 to 10% by weight.
• the cosmetically or dermatologically acceptable medium preferably consists of water or a mixture of water and cosmetically acceptable solvents such as monoalcohols, polyalcohols, glycol ethers or fatty acid esters, which can be used alone or as a mixture. Mention may more particularly be made of lower alcohols such as ethanol, isopropanol, polyalcohols such as diethylene glycol, glycol ethers, alkyl ethers of glycol or of diethylene glycol.
• the grafted silicone polymers according to the invention can be dissolved in said cosmetically acceptable medium or used in the form of an aqueous dispersion of particles.
• composition of the invention may also contain at least one additive chosen from thickeners, esters of fatty acids, esters of fatty acids and of glycerol, silicones, surfactants, perfumes, preservatives, sun filters , proteins, vitamins, polymers, vegetable, animal, mineral or synthetic oils and any other additive conventionally used in the cosmetic field.
• at least one additive chosen from thickeners, esters of fatty acids, esters of fatty acids and of glycerol, silicones, surfactants, perfumes, preservatives, sun filters , proteins, vitamins, polymers, vegetable, animal, mineral or synthetic oils and any other additive conventionally used in the cosmetic field.
• additives are present in the composition according to the invention in proportions which can range from 0 to 20% by weight relative to the total weight of the composition.
• the precise quantity of each additive depends on its nature and is easily determined by those skilled in the art.
• compositions according to the invention can be in the form of a gel, milk, cream, more or less thickened lotion or foam.
• compositions are more particularly styling lotions, brushing lotions, fixing compositions (lacquers) and styling.
• Lotions can be packaged in various forms, in particular in vaporizers, pump-dispenser bottles or in aerosol containers in order to ensure application of the composition in vaporized form or in foam form. Such forms of packaging are indicated, for example, when it is desired to obtain a spray, a lacquer or a foam for fixing or treating the hair.
• the compositions may also be shampoos, compositions to be rinsed or not, to be applied before or after shampooing, coloring, bleaching, perming or straightening.
• composition according to the invention when packaged in the form of an aerosol in order to obtain an aerosol lacquer or foam, it comprises at least one propellant which can be chosen from volatile hydrocarbons such as n-butane, propane , isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures. Carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air and mixtures thereof can also be used as the propellant.
• propellant can be chosen from volatile hydrocarbons such as n-butane, propane , isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures.
• Carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air and mixtures thereof can also be used as the propellant.
• the subject of the invention is also a process for the non-therapeutic treatment of keratin materials such as the hair, consisting in applying to them a composition as defined above and then optionally rinsing with water.

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• 1995
  • 1995-09-29 FR FR9511485A patent/FR2739285B1/fr not_active Expired - Fee Related
• 1996
  • 1996-09-16 US US08/983,343 patent/US6056945A/en not_active Expired - Fee Related
  • 1996-09-16 WO PCT/FR1996/001438 patent/WO1997012595A1/fr active IP Right Grant
  • 1996-09-16 CA CA002222309A patent/CA2222309C/fr not_active Expired - Fee Related
  • 1996-09-16 ES ES96931856T patent/ES2170869T3/es not_active Expired - Lifetime
  • 1996-09-16 BR BR9610835A patent/BR9610835A/pt not_active IP Right Cessation
  • 1996-09-16 DE DE69618651T patent/DE69618651T2/de not_active Expired - Lifetime
  • 1996-09-16 RU RU97121907/14A patent/RU2152783C2/ru not_active IP Right Cessation
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  • 1996-09-16 PL PL96324198A patent/PL185624B1/pl unknown
  • 1996-09-16 EP EP96931856A patent/EP0854703B1/fr not_active Revoked
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  • 1996-09-16 AT AT96931856T patent/ATE211381T1/de not_active IP Right Cessation
• 2000
  • 2000-04-04 US US09/542,293 patent/US6503494B1/en not_active Expired - Fee Related

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